| 官能团修饰的二维共价有机骨架中二氧化碳捕获与分离性能的理论计算 |
| Theoretical calculations of CO2 capture and separation by functional groups modified 2D covalent organic framework |
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| 摘要: 通过引入—OH、—NH2和—SO3H极性官能团，设计了具有高比表面积、亚胺键连接的二维三聚茚酮基共价有机骨架(truxenone-based covalent organic frameworks，TRO-COFs)，并通过巨正则蒙特卡洛(giant canonical Monte Carlo，GCMC)模拟和密度泛函理论(density functional theory，DFT)探究了298 K和0~1.0×105 Pa条件下极性官能团对TRO-COFs的CO2捕获性能的影响。结合能和内聚能的分析表明官能团引入后结构仍保持较高的稳定性。极性官能团的引入显著增强了TRO-COFs的CO2吸附性能。CO2吸附量大小顺序为TRO-COF-SO3H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H。在298 K和1.0×105 Pa条件下，TRO-COF-SO3H表现出8.02 mmol·g-1的CO2吸附量及CO2优于N2和CH4的选择性(37和26)。同时，通过径向分布函数和气体吸附密度分布也进一步说明了不同极性官能团对CO2捕获与分离性能影响的差异。最后，从吸附热、范德瓦耳斯力和库仑相互作用等多个角度详细阐明了极性官能团的作用机制。 |
| 关键词: 共价有机骨架 CO2捕获与分离 密度泛函理论 巨正则蒙特卡洛 |
| 基金项目: 管网集团(新疆)联合管道有限责任公司技术开发项目(No.GWXJLH22-2022-015)资助。 |
| Abstract: By introducing polar functional groups such as —OH, —NH2, and —SO3H, two-dimensional truxenonebased covalent organic frameworks (TRO-COFs) with high surface area and imine bond connections are designed. The influence of polar functional groups on the CO2 capture performance of TRO COFs is explored using grand canonical Monte Carlo simulation (GCMC) and density functional theory (DFT) at 298 K and 0-1.0×105 Pa. Analysis of binding energy and cohesive energy indicate that the functional groups modified TRO-COFs still maintain high structural stability. The introduction of functional groups significantly enhances the CO2 adsorption performance, with the order as follows: TRO-COF-SO 3H>TRO-COF-NH2>TRO-COF-OH>TRO-COF-H. Notably, TRO-COF-SO3H exhibits the highest CO2 adsorption capacity of 8.02 mmol·g-1 with a selectivity of CO2 over N2 and CH4 at 298 K and 1.0×105 Pa (37 and 26). Moreover, the different effects of functional groups on CO2 capture and separation are illustrated through the radial distribution function and adsorption density distribution. Finally, the modified mechanism of functional groups is elucidated from the heat of adsorption, van der Waals (vdW), and Coulomb interactions. |
| Keywords: covalent organic framework CO2 capture and separation density functional theory giant canonical Monte Carlo |
| 投稿时间：2024-06-04 修订日期：2024-09-13 |
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| 赵杰,张慧丽,鲁效庆,王兆杰.官能团修饰的二维共价有机骨架中二氧化碳捕获与分离性能的理论计算[J].无机化学学报,2025,41(2):275-283. |
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